Dialkyl 1-acylamino 2, 2-dichlorovinyl phosphates



United States Patent 3,183,258 DIALKYL l-ACYLAMINO 2,2-DICHLOR- VINYL PHOSPHATES Max Schuler, Arlesheim, Basel-Land, Hans Helfenberger,

Reinach, Basel-Land, and Karl Lutz, Basel, Switzerland, assignorsxto Sandoz A.G., Basel, Switzerland No Drawing. Filed Oct. 15, 1962, Ser. No. 230,683 Claims priority, application gygtlzerlrmd, Nov. 10, 1961-,

9 8 Claims. (Cl. 260-461) The present invention is concerned with new insecticidally active phosphoric acidesters. The invention is also concerned with use ofthe said esters and/or compositions containing the same, for combating pests, more especially insects. The invention is also concerned with a process for the preparation of the said new esters.

The new phosphoric acid esters of the present invention correspond to the formula or one of the groups -CH -NH- or O- forming together with R, members of a heterocyclic ring;

R is lower alkyl (e.g., methyl, ethyl, prOpyL-butyl, etc.),

or lower alkylene- (e.g., methylene, ethylene, propylene, etc.) connected with Y to form a heterocyclic ring (including N and X); I

R3 is CH3 or C3115; I

These new compounds I are prepared according to the presentinvention by reacting a compound of the formula wherein X, Y and R havevthe precedingly-recited significances, with a corresponding trialkylphosphite. The reaction is preferably carried out in a non-polar solvent medium and at raised temperature. Suitable non-polar solvent media are, for example, benzene, chlorobenzene, toluene, xylene, etc.

It is known from the literature that the reaction of trialkylphosphite with normal trichloroacetic acid amide yields no reaction products in the sense of a Perkow reaction (J.A.C.S. 82, 903 (1960)). It was therefore wholly unexpected and entirely surprising that the reaction of trialkylphosphite with a trichloracetic acid derivative of Formula IIshould take the form of a normal Perkow reaction, leading to products of Formula I. The trichoracetic acid derivatives of Formula II are not described in the literature, i.e., are new.

3,183,258 Patented May 11, 1965 Suitable compounds of Formula II for carrying out the process of the invention are for example N-trichloracetyl derivatives of methylformamide, N-methylurethane, N- methylacetamide, trimethylurea, trimethylsulfamide, pyrrolidone-2, piperidine-Z, ethyleneurea, etc.

The new compounds I are liquid at room temperature, and may be distilled'in ahigh vacuum. They are soluble in oils and in organic solvents and are readily converted into aqueous emulsion form. The new esters I are outstandingly suitable for combatting pests, particularly insects for the purpose of protecting plant growth.- They comprise compounds which are distinguished by excellent systemic action. ,1

For combating pests by means of the new phosphoric acid esters of Formula I, the latter are advantageously admixed with emulsifiers, for example with liquid polyglycolethers obtained from high molecular alcohols, mercaptans or alkylphenols by the adding on of ethylene oxide, the resultant mixture then emulsified in water, and the so-obtained aqueous emulsion applied by spraying onto the surface of the plants to be protected, or by watering the plants therewith. Solution aids, such as suitable organic solvents, for example monoor poly-alcohols, ketones, aromatic hydrocarbons, mineral oils, etc., may be addedto the aforesaid mixtures. In order to produce water-suspendible products, solid carrier materials such as talc, kaolin, kieselguhr, bentonite, etc.,' may also be incorporated into the said mixtures. The liquid or pul verulent products are emulsified or dispersed in water before being used, it being preferable that the obtained emulsions or dispersions contain 0.005 to 0.2% by weight of active ester I. o

However, the phosphoric acid esters I can also be used without emulsifiers, in which event they are advantageously admixed with adhesion'promoting agents and inert carriers such as talc, kaolin, kieselguhr, bentonite, etc., or with a mixture of such carriers, so that the product may be used as a dusting composition or scattering composition, containing, e.g., 0.5-5% active ester.

The following examples set forth presently preferred exemplary embodiments of the invention. Parts and percentages are by weight unless otherwise indicated. The relationship'of parts by weight to parts by volume is the same as that between grams and milliliters. Temperatures are in degrees centigrade.

EXAMPLES (A) Examples of the preparation of intermediates of the formula O=C-C0h 1 1' R. x i ((1) GENERAL METHODS One mol of a compound of the formula i (In) C. or else the said compound of Formula III, if desired in solution form, is added to the .trichloracetyl chloride. Thereafter stirring is continued for several more hours at elevated temperature until the reaction has gone to completion. The hydrogen chloride formed in the course of the reaction is continuously removed, advantageously by means of a gentle stream of gas, for example by passing a current of nitrogen or air into the reaction mixture. By distilling off the solvent, there is obtained the compound of Formula II as crude product, and the latter can be purified if desired by recrystallization or by distillation in high vacuum.

When, in the compound of Formula HI, Z stands for an alkali metal, the reaction components are brought to- Example 2.--9l parts of trichloracetyl chloride are added dropwise in the course of one hour to a suspension of 80 parts of the compound of the formula Na CH1 ong-r r-sm-n OH: in 350 parts by volume of benzene, the temperature being maintained throughout the said addition at 10 to by cooling. Thereupon stirring is continued for three more hours at 70. The precipitated NaCl is filtered ofi' warm and washed with warm benzene. By distilling the solvent from the filtrate, there is obtained from the latter the N-trichloracetyl derivative of the formula gether while cooling, for example at 0 to the tri- 15 0 1 CH1 chloracetyl chloride being added dropwise to a suspenc Ji o,

sion of the compound of Formula III, or the latter being CH added portionwise to the trichloracetyl chloride. The reaction is brought to completion at raised temperature, for 55.5 as g g i' i? g i fil g example at 50 to 100". In working up the reaction mass, 20 p y f T8 i5 5: i

separation from the formed ZCl is effected and the solav fi 1 6 8 vent is distilled off. The obtained crude product may be i 5 om o a f; {"3 i gt, f s

purified by recrystallization or by distillation under high 3 3 g a are 0 mm: ca c a e o p (b) SPECIFIC EXAMPLES 5 The same N-trichloracetyl compound of the formula Example 1.A. solution of I 24 parts of N-methyl- H acetamide in 20 parts by volume of trichlorethylene is 001v" stirred dropwise in the course of aboutone hour into a CH,

solution of 61 parts of trichlorae ty r e"? 0m is also obtained by reacting trichloracetyl chloride with y volume of trlhlorethylene, whlle mamtammg the so trimethylsulfamide in trichlorethylene. After stirring for action f f at the and under Iefiux, and there" 12 hours under reflux, the solvent is distilled OE and the after continuing the stirring under reflux for three more product is obtained, in a 73% i l as an almost l hours. After distilling, off the solvent, the product rs less Crystalline mass purified by distillation. There is thus obtained the N-tri- I anner analogous to any of the procedures -d- Chlofacetfi derivative of the fOrmula ing to the foregoing examples, the further N-trichlor- O CH acetyl derivatives set forth in the following table can also be prepared. The table lists the new derivatives of Fora I i. N- a mula II, characterizing properties, analytical data and, in a yield of about 90%; B.P. =5357; n =1.504O. in the last col t mp n ofFormula III which N calculated 6.4%; found 6.4%. 40 is reacted with the trichloracetyl chloride:

TABLE I Example No. Compounds II Properties Analyses Compounds III (I) C'H' CH3 3 CCl -(l-N-CHO B.P,..=so-52 Cl: cale.,52.2%;found,62.3%..... Z-i l-CHO O (EH5 Cant 4 CGlrCN--CHO B.P.n.05=48-50 N: calc.,6.4%;tound, 6.1% ZNCHO 5 CClrC-NCOCH; B.P-n.s=62-..... N: calc.,6.0%;'tound, 6.2% z-ts-cocm w r a, CCl;-C-NG'OOCH B.P.0.l=67 Cl: cale.,45.4%;lound,45..2%.... zN-c0ocH.

([3 (EH; I OH] 7 con-d-rr-ooocm. B.P.n=ll4 N: calc.,5.6% ;found, 5.4%..-.... z-N-0000,H,

(III) (hHr (72H: 8 CCll-C-N*-COOCHI B.P.0.l=-71 N: calm, 5.6%; found, 5.6%.-... zNc00cH O CaHr 01H; 9 CClz-iJ-NCOOC;H B.P.o.oi=74-76....--- N: calm, 5.3%;iound, 5.4% Z-N-COOChH;

(1) $11: CH; 10 C Ch-JJ-N-CO 01H Light yellow liquid--. N: calm, 6.0%; found, 5.9% Z-N- C 00,11

n,'=1.4999 H: (3H: 11 CClr--N-CO-NHCH: B.P. o ;86; Ml; N: calm, 12.0%; found, 12.4% ZN-'-CONHCH,

Example 22.-92.2 parts (0.4 mol) of the compound of the formula 6 TABLE I--Continued Example No. Compounds II Properties Analyses Compounds III (e) (e) 0 out on, on, out 12 CCl:( J-l ICO-N BP.o.o193 N: calm, 11.3%; found, 11.6% Z1 IC0N 7 CH3 GET; 0 CH3 C2115 CH: CgHs 13 CCls-( 3N-C0N Light-colored viscous CE: calm, 38.6%; found, 38.7% ZI I---C0N oil. N: calc., 10.1%; found, 10.0%.

1H: 01H 0 01H; on. 01115 on; 14 CCl3-CNSOz-N M.P.=6971 Z--NSO:N

I CH3 CH3 0 CH: elm CH3 0,11, 15 CClr-N-SOr-N Light yellow liquid..- N: (2110., 9.0%; found, 9.3% Zl ISOg-N CzHs CzH| CzHr 02H; 2 (3: 1 16 CCl3CNS02N B.P.o.2=117120 N: (1110., 8.6%; found, 8.6%.-- ZNSO:N

2 01H; CHr-CH': CHz-CH: 17 CClr-PJ N l B-P.0-1=106 N: calm, 6.1%; found, 6.4% ZN CO H: C 0 H: O CII CHg GHQ-CH 18 CCla( %N M.P.=77 C1: calm, 45.8%; found,45.4% Z-N OO-0 C0-- 0 0112-011, GH -HC, 19 CCIJ-HIN M.P.=1l4 N: calm, 12.1%; found, 12.0% Z-N CONH CO-NH CH3 CH; O (EH-CH1 H-CH: 20 CCls( )N M.P.=38 N: 0310., 5.7%; found, 5.7%-.. Z-N l \C 0-CH1 CO- H: 0 (IO-0H, CO-OH 21 CClzC-N 'CHn M.P.=84.. N: calm, 5.7%; found, 6.9% Z-N CH,

CHz--Ca GHQ-CH2 (B) Examples of the preparation and use of the endr 0 products of the formula -0-C=C01, R10 0 (311,0 fiN\ h 0-C=O(Jh G R10 I l 55 r" being obtainedin a yield of more than as a lightcolored O11 WhlCh can not be distilled m a high vacuum Y (1) without decomposition. N calculated 46%; found 4.6%.

Example 23.By following the procedure described in Example 22, the reaction between 69.2 parts of the compound of the formula 0 c Cl; N

and 52.3 parts of triethylphosphite, yields the compound of the formula CHa-C H3 7 be distilled in a high vacuum without decomposition. N calculated 4.2%; found 4.2%. Cl calculated 21.4%; found 21.5%.

Example 24.--27 parts of trimethylphosphite are added dropwise, at 50 to 60 and in the course of 10 minutes, to 5 a solution of 62.3 parts of the compound of the formula in 200 parts by volume of toluene, the mixture being stirred for one hour under reflux. The solvent is thereupon distilled otf, as well as readily volatile fractions, first under water-jet vacuum and then under a pressure of 0.2 mm. Hg and a bath temperature of 110. There is thus obtained in a 99% yield the compound of the formula as a light-colored liquid which can not be distilled in high vacuum without decomposition. N calculated 7.3%; found 7.5%. P calculated 8.0%; found 7.8%.

Example 25.--A solution of 46.5 parts of the compound of the formula in 150 parts by volume of toluene are added dropwise, at to and in the course of 15 minutes, to a solution of 35 parts by weight of triethylphosphite in parts by volume of toluene. Stirring is then continued for one I hour at 100-110, after which the solvent is distilled off under reduced pressure. There is thus obtained the compound of the formula CgHgO O N C CHO TABLE 11 Example No. Compounds I Properties Analyses (a) (b) (c) (d) CHzO O 26 -O-C=CC11 B.P. .1=103106 G]; calm, 25.6%; found, 25.7%.

OHaO I l C CHO CzHsO O 27 I OC=CCh B.P.u.oa=105108 C H O N CEh CHO 28 -OC=CC1; B.P. =112-116 P: calm, 10.6%; found 10.2%.

OHIO N CzHi CHO 0435 0 0 29 l 0-C=CC1 Non-distillable N: calm, 4.4%; found, 4.1%.

021350 N n =1A696 OIHB/ 830 01130 0 30 J OC=OCI: Non-dlstillable N: 01110., 4.8%; found, 4.6%. OHIO II I Cl: calc., 24.3%; found, 24.6.

CH; COCH:

C2 50 O 31 I E O- C=CC do CgH O N CH( COCH2 Table II-Continued Example No. Compounds I Properties Analyses CHaO [Oi 32; P-OC=C Ch Light yellowish oil N: 04510., 4.6%; found. 4.5%.

CHaO N\ v 0&6 c 0 0H.

C HgO O i] 33-. /P-OC=C Ch -do CsHaO v N CH: C O CH: CHaO\f[) '34 POC=CC]1 Light orange liquid N: calc..'4.6%; found, 4.2%.

. n,,'=l.4787 CHaO N ci l 0 0 CH:

CzHoO O ll 35 P0C=C Cl; Orange oil nn =1.4686 0211 0 N CHBO\?|) I 36 PO-C=CC1= Light-yellow liquid P1 calc., 10.1%; found, 10.2%.

I n.. =1.4787 Cl: calc., 23.1%; found, 22.8% C1120 N\ CH: C O 0 CH: CnHaO (i) 37 l 0C==C Ole Light yellow liquid v P: calc., 9.2%; found 9.6%.

I n,, =l.47l2 Cl: calc., 21.1%; found, 21.0%. (321150 /N\ CH3 C O O CH:

38 1OC=C Cl: B.P.o.o4=122l26 N: mic, 4.4%; found, 4.7%. n.. =1.4675 P calc., 9.6%; found, 9.7%.

CHaO N\ V CHa C 0 0 CnHl 39 --OC=CClg B.P.o.m=120-122 N: calm, 4.0%; found, 3.9%. i I n,, =1.4625 P: calc., 8.9%; found, 9.2%.

CH; C 0 0 Call,

C1330 40 I O-C=CC11 B.P.o.n2=123-1'Z5 Cl: calc., 21.1%; found, 21.5%.

. n =lA698 CHzO N\ 023.5 C O 0 Cali; C2 s0\fi 41 P--O-C=O Clo B.P.o.oo=132 N: 0510., 3.8%; found, 3.5%.

n =lAfi48 Cl: calc., 19.5%; found, 19.7%. 0 11 0 /N\ 02H; C 0 0 02H; C Hs0\(? 42 i-OC=C Cl; Light yellow oil Cl: calm, 22.0%; found, 22.4%.

nn =lA749 P: calm, 9.6%; found, 9.6%. C11 0 N\ C2115 C O 0 CH3 C2H50\ffi 43 PO-C=C 01 Light orange oil Cl: calm, 20.3%; found, 20.7%.

n. =1.4o50 P: calm, 8.9%; found, 8.7%. OM50 N 01H, 0 O O OH;

01130 (I? 44 P- -OC=C Cl, Light yellow oil N. 09.10., 9.1%; found, 9.3%.

CHaO N CH: C 0-NHCH3 Table Il-Continued Example No. Compounds I Properties Analyfles (a) (b) (c) (d) CzHsO O 45 -0-c=c c1, Light yellow oil N: 0310., 9.1%; found, 0.3%.

CgHO N CHa C ON HC Ha CH|O 0 C H O N CH:

C 111 C 0N C II:

C iii-I 0 O 47 POC=C Cl; Almost colorless oil N: calm, 8.0%; found, 8.1%.

O aH O N C H;

0113 C ON 01330 O 48 1 OC=C Cl; Light yellowish oil N: calc., 8.0%; found, 8.2%. CHaO N ca F: calc., 8.9%; found, 8.7%.

(1113 C ON C n a 021150 0 49 O-C=C Cl: Light yellowish oil N: calm, 7.4%; found, 7.3%.

P: 09.10., 8.2%; found 8.0%. 051150 N C1115 CH; O O-l/ \CHI 60 0-C=C Ch Light orange oil N: calm, 6.8%; found, 6.6%:

Cnllgo N C1116 Clh B Or-N 51 OC=CClz Weakly yellowish oil N: calm, 7.8%; found, 7.9%. P: 0810., 8.7%; found, 8.4%. CHgO N C H:

CH| B O:N

CIHgO O 52 O-C=C Ch do N: calc., 7.3%; found, 7.1%. P: calm, 8.0%; found, 7.7%. OIHBO N OH;

OH; 8 OzN OH;O 0 53 -0-C=C C11 Light orange oil N: calm, 7.0%; found, 7.3%:

0 I B a-N ClH 0 11 0 0 54 l -OC=C Ch do N: calc., 6.6%; found, 6.4%.

clmO I! C4115 \CBHD CHzO O 65 1 0C=C Cl: Light yellowish oil CHIO N Table II--Continued Oouipounds I Example No.

Properties I Analyses (a) on, co

CH2NII P-o c=cc1.

clmo N v 0%. co cub-1 :11

P oc=cc1,

011150 N i C \CO 611, cu,

i 0-c=c c1,

IIV CH3 soT-N Llfiht yellowish oil PO-C=C C1 do N:

Light brownish oi]..-..-

Light brown oil N:

Light orange oil N: 0510., 9.2%; found, 9.3%.

N: ealc., 4.4%; found, 4.6%. Cl: oalo, 22.3%; found, 22.7%.

calc., 4.0%; found, 3.9%. P: 0810., 9.0%; found, 8.9%.

01110., 4.4%; found, 4.2%.

calm, 4.0%; round, 4.0%.

: calc., 7.6%; found, 7.2%.

Example 64.-50 parts of the ester of the formula P-0C=C Cl: cn o 1's are admixed with 50 parts of isooctylphenyloctaglycolether, a clear solution being obtained. An aqueous solution of mixture, containing 0.05% of the ester, is sprayed onto young apple trees infested with aphis. In a few hours, all the aphis have been killed.

Example 65 parts of the ester of the formula P-0-c=oc1,'

0H, 000011, are admixed with parts of isooctylphenyloctaglycolaHtO ether and parts of a petroleum fraction which boils at 210-280", specific gravity (20) 0.92, a clear solution being obtained which is well emulsifiable in water. Such an emulsion, containing 0.02% of the ester, effects a kill on aphi's.

C HgO are admixed-with 20 parts of laurylhexaglycolether and 60 parts of xylene, the resultant product being readily water-emulsifiable. A 0.1% aqueous emulsion of this product, which emulsion contains 0.02% of the said ester, is sprayed onto potted plants (Cineraria, asters (chrysanthemums) infested with aphis. In a short time, all aphis.

are dead.

Example 67.-(a) By admixing 25 parts of the ester of the formula with 25 parts of diisohexyl-heptylphenylhexaglycolether, 25 parts of xylene and 25 parts of diethyleneglycol, a product is obtained which is well emulsifiable with water. Potted spiderwort plants of a height of about cm. are each watered with 100 milliliters of an aqueous emulsion of the said product, such emulsion containing 0.02% of the active ester, care being taken that no green parts of the plant are wetted. The next day, 30 grasshopper larvae (Carausius morosus), second stage, are applied to each plant. The larvae feed on the leaves and in this way also include in their nourishment the aforesaid active ester which has been taken in by the roots of the plants and transported to the leaves. At the end of 8 days, no living larvae remain; all are dead.

(b) A 0.1% aqueous emulsion of the same product, said emulsion containing 0.025% of the active ester, is sprayed on aphis-infected plants of Erigeron canadense, in such manner that only the bottom part of the plants (not roots) are contacted, while the upper part of the plants-where the aphis areremains untreated. After 2 to 3 days, all aphis on the not-directly treated upper part are dead.

(c) Bean plants in the two-leaf stage and which are infected with Aphis fabae are sprayed with an aqueous emulsion of the same productwhich emulsion contains 0.04% of the said active ester whereupon, in a few hours, all the aphis have been killed.

(d)The active ester of formula used in paragraphs (a) to (0), can be replaced by corresponding amount of the ester of formula CHaO O whereupon the same successful results will be achieved.

Example 6.A pulverulent product of good suspend- 16 ability in water is obtained by intimately admixing 15 parts of the ester of the formula c,mo t

i -o-c=cc1,

0 a with 3 parts of tert. dodecylmercaptanundecaglycolether, 7 parts of powdered silica gel and parts of kaolin. A suspension prepared from this mixture and containing 0.1% of the said ester, when sprayed on aphis, effects a complete kill in a few hours.

Example 69.2 parts of the ester of the formula CIHIO are admixed with 98 parts of talc, and the mixture ground in a ball mill. The resultant product is a dusting agent which, dusted on areas infected by cockroaches (Periplaneta americana), etfects a 100% kill in 24 to 48 hours of all the roaches which come into contact with the dust.

Having thus disclosed the invention, what is claimed is:

1. A compound of the formula alkyl-O o -o-c=c or,

wherein X is a member selected from the group consisting of alkyl-O alkyl and Y is a member selected from the group consisting of H, alkyl, O-alkyl, --N(alkyl) and NI-I(alkyl), alkyl being throughout alkyl with a maximum of two carbon atoms.

2. A compound of the formula aIkyl-O\(l? P-0-c=cct,

alkyl C 0 kyl wherein each alkyl has a maximum of two carbon atoms.

3. A compound of the formula alkyl-O wherein each alkyl has a maximum of two carbon atoms.

alkyl-O 17 18 5. A compound of the formula Cure,

alkyI-O \u c0- 11, aikyi-o N 5 cu -4:112

alkyl (30 I N1'I(a1kyl) I wherein each alkyl has a maximum of two carbon atoms. CHPCH, .6.A.com'pound of the'formula v N alkyl-O fi r P -O-C=C c1, CO*NH a1k'y10 /N\ E CH alkyl 10 N H v N(a1l;y1)a wherein each alkyl has a maximum of two carbon atoms. 00-

7. A compound of the formula and alkyl-O o o0-o1r,

i -o co C11 N ulkylO 1 elm-0H,

mkylz i I and each alkyl has a maximum of two carbon atoms. NWkYlh References Cited by the Examiner wherein each alkyl has a maximum of two carbon atoms. UNITED STATES PATENTS A compwnd of the fmmula 2,801,200 7/57 Hackmann 167-22 Q? 2,802,855 8/57 Whetstone et a1 260-461 POC=C (11 2,865,912 12/58 Pohlemann et a1 260326.5 alkym/ l, 2,938,831 5/60 Gordon 167-33 i 2,968,591 1/61 Tracy 16722 wherein v FOREIGN PATENTS 783,697 10/53 Great Britain.

l I CHARLES B. PARKER, Primary Examiner.

represents a member selected from the group consisting of IRVING MARCUS, Examiner. 

1. A COMPOUND OF THE FORMULA
 8. A COMPOUND OF THE FORMULA 